The term “butyl rubber” as used herein generally means and encompasses co-polymers of C4 to C7 isoolefins, C4 to C14 conjugated dienes and optionally other co-polymerizable monomers, if not defined otherwise. The term “bromobutyl rubber” as used herein generally means and encompasses brominated butyl rubbers if not defined otherwise. An illustrative and preferred example of butyl rubber is a rubber obtained by co-polymerization of isoprene and isobutylene, which is hereinafter also referred to as IIR. Its brominated analogue is also referred to as BIIR.
Poly(isobutylene-co-isoprene), or IIR, is a synthetic elastomer commonly known as butyl rubber which has been prepared since the 1940's through the random cationic copolymerization of isobutylene with small amounts of isoprene. The resulting commercially available IIR, has a multiolefin content of between 1 and 2 mol %. As a result of its molecular structure, the IIR possesses superior air impermeability, a high loss modulus, oxidative stability and extended fatigue resistance (see Chu, C. Y. and Vukov, R., Macromolecules, 18, 1423-1430, 1985).
It has been shown that treatment of bromobutyl rubber with nitrogen and/or phosphorus based nucleophiles leads to the generation of ionomers with interesting physical and chemical properties, which are dependent inter alia on their initial isoprene content (see EP 1 922 361 A, EP 1 913 077 A, Parent, J. S.; Liskova, A.; Whitney, R. A.; Parent, J. S.; Liskova, A.; Resendes, R. Polymer 45, 8091-8096, 2004, Parent, J. S.; Penciu, A.; Guillen-CasteUanos, S. A.; Liskova, A.; Whitney, R. A. Macromolecules 37, 7477-7483, 2004.
Polymer nanocomposites is a rapidly expanding, multidisciplinary field that represents a radical alternative to conventional-filled polymers or polymer blends. Polymer nanocomposites are typically formed by the incorporation of nanosized fillers into a ionomer matrix. Hybrid materials reinforced with neat and/or organically modified high aspect ratio plate-like fillers represent the most widely studied class of nanocomposites. Strong interfacial interactions between the dispersed layers and the polymer matrix lead to enhanced mechanical and barrier properties over the conventional composite. Among the many areas of polymer nanocomposites research, the tire industry has become particularly interested in high aspect ratio fillers. Recent studies have shown that the addition of high aspect ratio fillers in tire inner liner formulations have shown an increase in impermeability of up to 40% (see, for example, U.S. Pat. No. 7,019,063 and EP 1 942 136 A.
Maximizing high aspect ratio fillers to their highest potential requires the correct morphology, making the selection of both the polymer and the filler critical. Polymer intercalation into the platelet galleries, delamination and exfoliation of the platelet and the anisotropic alignment of plates in the rubber matrix must be achieved. In order to accomplish at the very least the intercalation and delamination, it is advantageous to establish a chemical link between the polymer matrix and the filler surface.
The ionomers, in particular the butyl ionomers, used to prepare polymer nanocomposites are typically prepared in a multistep procedure comprising a slurry polymerization, solution halogenation and a kneading reaction to form the ionomers and the nanocomposites.
In the conventional slurry process for producing bromobutyl rubber, isobutylene and isoprene monomers are first polymerized in a polar halohydrocarbon medium, such as methyl chloride with an aluminum based initiating system, typically either aluminum trichloride (AlCl3) or ethyl aluminum dichloride (EtAlCl2). The butyl rubber does not appreciably dissolve in this polar medium, but is present as suspended particles and so this process is normally referred to as a slurry process. Residual monomers and polymerization medium are then steam stripped from the butyl rubber, before it is dissolved in a bromination medium, typically a non-polar medium such as hexane. The bromination process ultimately produces the final brominated product. The conventional process therefore employs separate polymerization and bromination steps employing two different media. The use of a polar medium for polymerization and a non-polar medium for bromination necessitates intermediate stripping and dissolving steps and is inefficient from an energy point of view.
The step of separating the monomers and methyl chloride from the butyl polymer is conducted before bromination in order to avoid the formation of highly toxic byproducts from the reaction of bromine with residual monomers. The normal boiling points of the components used in the process are: methyl chloride, −24° C.; isobutylene, −7° C.; and, isoprene, 34° C. Any stripping process that removes the heavier of the residual monomers (isoprene) will also remove essentially all of the methyl chloride and isobutylene. The process of removing all of the un-reacted components from the rubber slurry requires significant amounts of energy. The greater molecular weight (and therefore higher boiling point) of the brominated monomers also precludes the removal of these species following the bromination process.
Solution processes for the polymerization of butyl rubber have been known for many years and are practiced commercially in Russia. An example of the solution process is described in CA 1,019,095, which discloses the use of iso-pentane as the preferred polymerization medium. The polymers produced using the above process are non-halogenated. Although bromination could theoretically take place in iso-pentane, the presence of residual monomers (isobutylene and isoprene) would lead to formation of the afore-mentioned undesirable by-products during bromination. The removal of the un-reacted monomers is the challenge for such a process and has not been resolved yet. Although it would be desirable to remove the monomers by distillation, the boiling point of iso-pentane (28° C.) is lower than that of the heavier residual isoprene monomer (34° C.), therefore this kind of separation is impossible. Even if pure n-pentane (boiling point 36° C.) were used as the medium, the difference in boiling points would be insufficient to allow effective removal of the isoprene using distillation techniques. As a result, the residual monomers and medium would all have to be stripped together from the butyl rubber, as in the slurry process, with the rubber being subsequently re-dissolved for bromination. This is, in fact, more energy intensive than bromination from the conventional slurry process. The use of iso-pentane as a common medium for producing bromobutyl rubber is therefore not practical using the conventional solution process.
It is known in the art to use hexane i.e. a C6 medium as a polymerization medium in the solution process. However, the viscosity of a polymer solution is strongly dependent upon the viscosity of the medium used. Because the viscosity of a C6 medium is much higher than that of a C5 medium, for a given molecular weight and polymer solids level, the resulting viscosity of the polymer solution is also much higher. This limits polymer solids content to relatively low levels when C6 is used as a solvent, since otherwise the solution becomes too viscous for good heat transfer, pumping and handling. The overall economics of a process depend strongly on the level of polymer solids in the solution or suspension emerging from the polymerization reactor; higher solids levels mean higher conversion and improved economics. In order to make material having a sufficiently high molecular weight for commercial purposes, it is necessary in butyl polymerization to employ relatively low temperatures, often less than −80° C. These low temperatures exacerbate the problem of high solution viscosity and lead to even lower solids levels. In the solution process, it is therefore quite difficult to achieve an economic solids level (conversion) at the desired temperature (molecular weight) when using hexane as a solvent due to high viscosity.
In U.S. Pat. No. 5,021,509 a process is disclosed whereby product from the conventional slurry polymerization process is mixed with hexane to produce a crude rubber solution or cement. The hexane is added to the methyl chloride-rubber slurry after exiting the polymerization reactor in order to dissolve the rubber in hexane while still finely divided and suspended in the methyl chloride/monomer mixture. A distillation process is then used to remove methyl chloride and residual isobutene and isoprene monomers for recycle, leaving just the rubber in a hexane solution ready for halogenation. This so-called “solvent replacement” process still requires that all of the original media left with the rubber after the polymerization stage are removed. The energy requirement is essentially the same as in the conventional process. No common solvent is employed for both polymerization and bromination.
Consequently, there still remains a need for an efficient, environmentally favourable process for the preparation of brominated rubbers which may then be further converted to nanocomposites.